Pairwise learning refers to learning tasks where a loss takes a pair of samples into consideration. In this paper, we study pairwise learning with deep ReLU networks and estimate the excess generalization error. For a general loss satisfying some mild conditions, a sharp bound for the estimation error of order $O((V\log(n) /n)^{1/(2-\beta)})$ is established. In particular, with the pairwise least squares loss, we derive a nearly optimal bound of the excess generalization error which achieves the minimax lower bound up to a logrithmic term when the true predictor satisfies some smoothness regularities.